Photographic material containing a filter dye

ABSTRACT

A LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL INCLUDING A DYE CORRESPONDING TO THE FORMULA:   1-R2,3-R1,4-((NC-(CH2)N-)2-N-A-CH=)-2-PYRAZOLIN-5-ONE   WHEREIN: A IS AN ARYLENE NUCLEUS, OR AN ARYLENE NUCLEUS FORMING PART OF A FUSED RING SYSTEM, EACH OF R1 AND R2 IS AN ARYL GROUP, AT LEAST ONE OF SAID ARYL GROUPS BEING SUBSTITUTED DIRECTLY OR OVER -O-, -S-, -SO-, -SO2-,   -SO2-N(-R)- GROUP, -CO-, -COO- OR A -N(-R)- GROUP   WHEREIN R REPRESENTS HYDROGEN OR AN ALKYL GROUP, WITH AN ALKYL GROUP OF 5 TO 20 CARBON ATOMS, AND N REPRESENTS, 1, 2, OR 3 IS DESCRIBED. THE PHOTOGRAPHIC MATERIALS HAVE EXCELLENT SPECTRAL ABSORPTION CHARACTERISTICS FOR FILTER PURPOSES AND ARE VERY RESISTANT TO DIFFUSION.

Feb. 16, 1971 DEPOQRTER ETAL 3,563,748

' PHOTOGRAPHIC MATERIAL CONTAINING A FILTER DYE Filed Feb. 15, 1967 3 Sheets-Sheet 1 0.0| lllllllll|1lll| Feb. 16, 1971 DEPOQRTER EI'AL 3,563,748

PHOTOGRAPHIC MATERIAL CONTAINING A FILTER DYE Filed Feb/L5, 1967 3 Sheets-Sheet 2 Feb. 16, 1971 DEPOORTER ETAL 3,563,748

PHOTOGRAPHIC MATERIAL CONTAINING A FILTER DYE Filed Feb. L5, 1967 v I 3 Sheets-Sheet I United States Patent 3,563,748 PHOTOGRAPHIC MATERIAL CONTAINING A FILTER DYE Henri Depoorter, Mortsel-Antwerp, Guy Alfred Rillaers, Kontich, Felix Jan Moelants, Wilrijk-Antwerp, and Theofiel Hubert Ghys, Kontich, Belgium, assignors to Gevaert-Agfa N.V., Mortsel, Belgium, a Belgian com- Filed Feb. 15, 1967, Ser. No. 616,343 Claims priority, application Great Britain, Mar. 3, 1966, 9,351/ 66 Int. Cl. G03c N84 US. CI. 96-84 6 Claims ABSTRACT OF THE DISCLOSURE A light-sensitive photographic material including a dye corresponding to the formula:

wherein A is an arylene nucleus, or an arylene nucleus forming part of a fused ring system,

each of R and R is an aryl group, at least one of said aryl groups being substituted directly or over O, S, 'SO, -SO

a SOzlTI- group, lh3, (|?O or a IIQ group wherein R represents hydrogen or an alkyl group,

with an alkyl group of 5 to carbon atoms, and n represents 1, 2, or 3 is described. The photographic materials have excellent spectral absorption characteristics for filter purposes and are very resistant to diffusion.

This invention relates to a new class of dyes, to the preparation thereof and to their use in photographic materials.

As is known, it is necessary to provide in common photographic colour material a filter layer, which absorbs the blue light, between the blue-sensitive silver halide emulsion layer and the green-sensitized silver halide emulsion layer. This filter layer must meet a whole series of requirements. Summarized, the filter layer should have a well-determined absorption range corresponding to the inherent sensitivity range of the underlaying emulsion layer(s), it should be stable and photographically inert in respect of adjacent layers, the dyes incorporated therein should be fast to diflusion and be easily discharged during processing. Up to now no product, composition or material is known which simultaneously and fully meets the above requirements.

A colloid layer comprising colloidal silver is almost generally used since with this kind of layer the above requirements are best met. However, such layer does not possess the desired absorption characteristics in full and the colloidal silver therein may give rise to fog in the adjacent silver halide emulsion layers. Further, as known to one skilled in the art, a filter layer containing colloidal silver may give rise to difficulties in negative sound track copying on a duplicating reversal colour material.

Organic dyes have been proposed as substitutes for colloidal silver. Many classes of dyes, however, were al- Patented Feb. 16, 1971 ways, in at least one respect, inferior to colloidal silver particularly as to the discolouration in photographic baths, so that additional baths e.g. containing a reducing agent such as hydrazine are prescribed in order to still obtain an acceptable discolouration.

It is an object of the present invention to provide a new class of dyes, which are discharged as easily as colloidal silver in the usual processing baths, do not induce fog in the adjacent layers, have excellent spectral absorption characteristics for filter purposes and are very resistant to diiiusion.

The dyes according to the present invention are represented by the following general Formula I A represents an arylene nucleus which may be substituted or condensed to form a fused ring system preferably however a phenylene radical which may be substituted e.g. with an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a halogen atom, a nitro group, a carbalkoxy group, a carboxy group, a cyano group, a sulpho group, an alkylsulphonyl group, an amido group, a sulfonamido group, a mercapto group, or an alkylmercapto group,

each of-R, and R represent an aryl group at least one of the aryl groups being substituted, directly or over a bivalent radical such as a -O-, S, SO, -SO

SO2l I, C O-, C O O, or a l I- group (wherein R represents a hydrogen atom, or an organic radical eg. an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group or a cycloalkyl group) by an alkyl group, and n represents 1, 2 or 3.

The structural formulae of some examples of dyes corresponding to general Formula I are listed in the following table.

TABLE N C-CHz-Cz N C-OH CH 2 2 O NC-CHz-CHz f -Q-ocmcm Nc-cm orn NC-CHz-CHz OCHz F -oH=c J-- :H2)-cm The dyes according to the present invention can be prepared by allowing to react a compound of the general NC-CHz-CEa N z R N C O w m r m u w m C O N F 5 0 6 7 m w m n wherein R and R have the same value as in Formula I, with an aldehyde of the Formula III NC(C 2) III wherein A and n have the same value as in Formula I. The reaction is preferably carried out in the presence of an inert solvent such as methanol, ethanol, butanol, ethylene glycol monomethylether, dimethylformamide, dimethyl sulfoxide and tetrahydro thiophene-l,l-dioxide.

The following illustrates the preparation of intermediates for the preparation of said dyes without, however, limiting the scope of our invention thereto.

PREPARATION A A warm solution of 20.1 g. (0.05 mole) of methy1-4 cetyl-benzoylacetate in 80 ml. of ethylene glycol monomethyl ether is added to a warm solution of 9.4 g. of 4-su1pho-phenylhydrazine and 7 g. of sodium acetate (trihydrate) in 30 ml. of water. The mixture is refluxed for 90 min. with stirring. After cooling, the pyrazolone is collected, washed with a little of water, methanol and ether and dried at 70. Yield: 18 g. (64%). Melting point: above 260 C.

In a similar way are prepared:

SOQNa S OiNB.

SONa o=o \N I a TOaNa SIOaNa PREPARATION B 02( 2)1aOHa o=c N H.t t To a warm solution of 86.4 g. of 4-cetylsulphonylphenylhydrazine hydrochloride in 300 ml. of ethanol, 54 g. of ethyl-3-fluorosulphonyl-benzoyl acetate is added. After 15 min. of refluxing, 32 ml. of pyridine is added and refluxing is continued for 30 min. After having added 150 ml. of water followed by cooling, the precipitate is collected and dissolved in 1 litre of acetone. While stirring and gently boiling, a solution of 40 g. of potassium hydroxide in 120 ml. of water is added dropwise. Then ml. of acetic acid are added dropwise whereupon the mixture is refluxed for 5 min. and cooled and the product is collected and dried. Yield: 66%.

In a similar way is prepared:

SIOaNa SOsNB PREPARATION C O2-( 2)1sCHa A mixture of 39.6 g. of 4-cetylsu1phonyl-phenylhydrazine and 29.2 g. of ethyl-4-fluorosulphonyl-benzoylacetate is heated for 1 hour at -125". The reaction product thus obtained is recrystallized from 1 litre of methanol. The fluorosulphonyl group in the pyrazolone so obtained is converted into a sulpho group as described in preparation B.

In a similar way are prepared:

PREPARATION l The dyestuff of Formula 1 of the above table is prepared as follows:

A mixture of 6.8 g. of the pyrazolone of preparation B, 2.5 g. of 4[bis (2 cyanoethyl)a1nino Jbenzaldehyde and 50 ml. of pyridine is refluxed for 2 hours and then evaporated under diminished pressure. The residue is recrystallized from ethanol. Yield: 6 g. (70% Absorption maximum: 456 nm. in methanol. :2.63 X

PREPARATION 2 The dyestuff of Formula 5 of the above table is prepared as follows:

A mixture of 5.7 g. of the pyrazolone of preparation A,

2.3 g. of 4[bis(2-cyanoethyl)amino-]benzaldehyde and 50 ml. of dimethyl-formamide is refluxed for 5 hours and then evaporated under diminished pressure. The residue is recrystallized from 75 cc. of methanol. Yield: 5.1 g. (60%). Absorption maximum (in methanol): 432 nm. e: 3.71 X 10 The dyestuffs listed in the following table were prepared analogously to those of preparations 1 and 2 above.

Abs. max. Yield (nm.) (in (percent) methanol) 6 Dyestuff of Formula:

60 457 2. 98X10 77 445 2. 77X10 66 455 1. 00x10 76 433 4. 33 10 68 433 3. 80X10 62 433 2. 46 l0 47 435 3. 88X10 52 438 2. 01X10 65 435 3. 68XI0 54 445 3. 53X10 60 450 3. 96X10 68 435 3. O9X10 Although, as said above, the dyestuffs according to the invention are excellently suitable for use in a yellow filter layer between the blue-sensitive layer and the green-sensitized layer of a photographic colour material it is evident that they can also be applied in any photographic material based on light-sensitive silver halide where easily dischargeable, non-migratory yellow dyestuffs are desired or necessary. Examples of other applications of these dyes are: in an antihalation layer between the support and a light-sensitive silver halide emulsion layer, in a filter layer between two light-sensitive silver halide emulsion layers or as screening dye in a light-sensitive layer.

The dyes according to the present invention can be incorporated into a photographic material according to techniques known by those skilled in the art for incorporating e.g. colour couplers and optical sensitizers.

The dyestutf is for instance dissolved in an appropriate solvent (in most cases this solvent can be water) and then added to a gelatin solution. To this solution can also be added appropriate coating aids and hardening agents. The solution thus obtained can then be applied as a layer according to known processes.

In the following table are listed the amounts of the dyes described above which have to be used in a gelatin colloid layer to obtain an optical density equal to 1.0, measured at the )t observed for the dyestuff in question.

Mg. dye X max. stufi/sq. m. (nm.)

Dyestutf of Formula:

Example 1 A coating solution of the following composition:

Inert gelatin 10 Dyestuff 7 3 Chrome alum 0.2 Sodium 2-methyl-7-ethylundecane sulphate 0.375 Distilled water up to 600 and having pH 5.62, is coated on a subbed cellulose triacetate support pro rata of 60 g./sq.m. so that 1 g. of gelatin and 300 mg. of dyestuff are present per sq.m. The spectral absorption characteristics of the layer obtained are represented in FIG. 1.

This solution can be used for providing in a conventional way a yellow filter layer between the green-sensitized and the blue-sensitive silver halide emulsion layers of a multilayer colour material. With the above mentioned concentration of dyestutf the greenand red-sensitized silver halide emulsion layers are sufficiently shielded against light corresponding to the inherent sensitivity of said layers.

Example 2 This example is analogous to Example 1 with the difference however that 4.125 g. of dyestutf 9 are used instead of 3 g. of dyestulf 7.

In this way a material is obtained, the filter layer of which comprises per sq.m. 1 g. of gelatin and 412.5 mg. of dyestuff 9. The absorption characteristics of this layer are represented in FIG. 2.

Example 3 A coating solution intended for providing an antihalation undercoat containing a non-migratory dyestuff has the following composition:

Inert gelatin30 g.

Saponine0.6 g.

4% formaldehyde- 0.75 ml. Demineralized water up to 1000 g.

This solution ready for coating has pH 6.1.

The solution is applied to a subbed polyethylene terephthalate support pro rata of 70 g./sq.m. so that 2.1 g. of gelatin and 0.280 g. of dyestuff are present per sq.m. The spectral absorption characteristics of the layer obtained are represented in FIG. 3.

Afterwards, a non-sensitized silver halide emulsion layer may be applied to the above antihalation layer. The coloured undercoat assures an excellent antihalation action in respect of the emulsion applied without adversely affecting the sensitivity of the emulsion. The antihalation layer discolours completely after a treatment in the classical black-and-white developing and fixing baths.

We claim:

1. A light-sensitive photographic element comprising a light-sensitive silver halide material and a dyestuff corresponding to the formula:

wherein:

A is an arylene nucleus, or an arylene nucleus form ing part of a fused ring system, each of R and R is an aryl group, at least one of said aryl groups being substituted directly or over O, --S-, SO, -1SO wherein R represents hydrogen or an alkyl group, with an alkyl group of 5 to 20 carbon atoms, and

n represents 1, 2, or 3 in a light-sensitive silver halide emulsion layer, a water permeable colloid anti-halation or filter layer.

2. A light-sensitive photographic material according to 7 claim 1 wherein R or R are substituted with a sulpho group in acid or salt form.

3. A light-sensitive photographic material according to claim 2 wherein the dyestulf corresponds to one of the following structural formulae:

SIOaNa 4. A light-sensitive photographic element according to claim 1 including a water-permeable colloid anti-halation layer which contains said dye.

5. A light-sensitive photographic element according to claim 1 including at least one light-sensitive silver halide emulsion layer.

6. A light-sensitive element according to claim 1 Wherein the light-sensitive material is included in a water-permeable colloid layer.

References Cited UNITED STATES PATENTS 2,688,540 9/1954 Ganguin et al. 9684 2,688,541 9/1954 Ganguin et al. 9684 2,709,136 5/1955 Ganguin et al. 96-84 3,316,091 4/1967 Rossi et al. 96-84 RONALD H. SMITH, Primary Examiner US. Cl. X.R. 

